JP4531039B2 - Hydrophobic process for textile materials - Google Patents

Abstract

Process for finishing textile materials involves treatment with aqueous liquor(s) (I) containing organic polymer(s) (II) and not less than 5.5 g/l particulate (in)organic solid(s) (III). Independent claims are also included for the following: (1) (I) per se; (2) production of (I) by mixing (II), (III), water, optionally organic solvent(s) and optionally other components, so that the (III) concentration is not less than 5.5 g/l; (3) formulation (IV) containing (II), (III), optionally organic solvent(s), optionally emulsifier(s) and 0-15 wt.% water.

Description

  The present invention is a method for finishing a textile material by treating the textile material with at least one aqueous liquid comprising at least one organic polymer and at least one organic or inorganic particulate solid. And an organic or inorganic solid is present in the aqueous liquid at a rate of at least 5.5 g / L (liter).

Textile finishing is an area that is becoming commercially important. In particular, it is of great interest to finish the fabric in order to keep out water and dirt (sewage). Modern methods, in some cases, utilize so-called Lotus-Effect ^R and impart water repellency to the fabric by applying a rough surface.

Patent Document 1 (WO 96/04123) discloses a self-cleaning surface having a processed uneven surface structure. This structure is particularly characterized by its structural parameters. This structure, for example, by applying a Teflon powder thermoplastically or embossing a specific structure capable of forming a hydrophobic material, or UHU ^R in the treated surface, is manufactured. Patent Document 2 (US Pat. No. 3,535,022) discloses a water-repellent surface produced in the same manner.

  In Patent Document 3 (EP-A0933388), first, a negative mold is manufactured by photolithography, a plastic film is embossed using this mold, and then the embossed plastic film is hydrophobized with fluorinated alkylsilane. A method of manufacturing a structured surface comprising is disclosed.

  However, the above-described method is not suitable for finishing the fabric without filth (sewage) and water.

Patent Document 4 (WO02 / 84013), the fibers of polyester, a method of hydrophobic fibers of polyester by drawing through a hot decalin bath 1% Aerosil ^R 8200 hydrophobized silica gel has been suspended (80 ° C.) Proposed.

Patent Document 5 (WO02 / 84016), a woven polyester fabric, 1% of the fabric by the pulling out through Aeroperl ^R 8200 hot hydrophobic silica gel was suspended DMSO bath (dimethyl sulfoxide) (50 ° C.) There has been proposed a method for hydrophobizing.

  These two hydrophobization methods have the common feature that the solvent is selected so that the fibers partially dissolve. This requires the use of large amounts of organic solvent and is often undesirable. Furthermore, treatment with organic solvents affects the mechanical properties of the fiber.

  In Patent Document 6 (WO01 / 75216), by providing a two-component layer such as a dispersion medium on one side and a colloid or the like on the textile fiber and the fabric, water and filth (sewage) are kept away from the textile fiber and the fabric. A method to make it is proposed. In the finishing method described in Patent Document 6, since it is observed that the colloid is concentrated in the boundary layer between the finishing layer and the surrounding surface, the finishing layer in which the colloid is anisotropically dispersed in the dispersion medium. Is provided. This method uses a finishing solution containing 5 g / L or less Aerosil-812S.

  However, in many cases, the fabric finished by the method described in Patent Document 6 does not have satisfactory mechanical strength.

WO96 / 04123 US3354022 EP-A0933388 WO02 / 84013 WO02 / 84016 WO01 / 75216

  Accordingly, an object of the present invention is to provide a method for finishing a woven material that does not have the above-mentioned disadvantages and gives excellent performance (water repellency, soil repellency) that keeps water and dirt (sewage) away. is there. Furthermore, another object of the present invention is to provide a fabric that keeps away water and filth (sewage). Yet another object of the present invention is to provide a liquor for finishing the textile material so that it does not attract water and dirt (sewage).

  The inventors have found that the above object is achieved by the method defined at the beginning.

  The textile material of the present invention is on the one hand fibers, rovings, yarns, threads and on the other hand textile fabrics such as woven fabrics, knits, non-woven fabrics and garments. It is. Woven fabrics used for the production of outdoor fabrics are preferred. Examples of outdoor fabrics include sails, umbrellas, waterproof fabrics, ground sheets, tablecloths, and furniture covers for chairs, swings, benches, and the like.

  The textile material of the present invention can be composed of different substances. For example, natural fibers and synthetic fibers, and further mixed fibers. Examples of natural fibers include silk, hair and cotton. Examples of synthetic fibers include polyamide, polyester, polypropylene, polyacrylonitrile, polyethylene terephthalate, and viscose. Similarly, modified natural fibers can be coated according to the method of the present invention, for example cellulose acetate.

  The method of the present invention utilizes at least one aqueous liquid. The aqueous liquid of the method of the present invention also includes a liquid that can contain at least 5% by mass of water. The water content of the aqueous liquid is preferably at least 25% by weight, more preferably at least 50% by weight, particularly preferably at least 75% by weight. The maximum water content is 99% by mass, preferably 97% by mass, more preferably 95% by mass.

  The aqueous liquid used in the present invention is an organic solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol. , N-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers, and further water. The organic solvent can occupy 1 to 50% by mass, preferably 2 to 25% by mass, of the aqueous liquid of the present invention.

  At least one liquid used in the method of the present invention contains at least one organic polymer. The organic polymer can act as a binder. The action of the binder is brought about by the organic polymer forming, for example, a film that bonds the particles together and bonds the particles and the textile material to be coated.

  In one embodiment of the present invention, the at least one organic polymer can include a polymer or copolymer of an ethylenically unsaturated hydrophobic monomer having a water solubility at 25 ° C. of less than 1 g / L. . In the copolymer, the hydrophobic monomer accounts for at least 50% by weight, preferably 75% by weight of the copolymer.

Preferred monomers are the following groups:
C ₂ -C ₂₄ -olefins, in particular α-olefins having ₂ to ₂₄ carbon atoms, such as ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene or 1-octadecene;
Styrenes such as styrene, α-methylstyrene, cis-stilbene, trans-stilbene;
Diolefins such as 1,3-butadiene, cyclopentadiene, chloroprene or isoprene;
C ₅ -C ₁₈ - cycloolefins, such as cyclopentene, cyclohexene, norbornene, dimerized cyclopentadiene;
Linear or branched C ₁ -C ₂₀ - vinyl esters of alkanoic acids, such as vinyl acetate, vinyl propionate, n- butanoate vinyl, n- vinyl hexanoate, n- octanoic acid vinyl, vinyl laurate and stearate vinyl;
C ₁ -C ₂₀ - (meth) acrylic acid esters of alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n- propyl (meth) acrylate, isopropyl (meth) acrylate, n- butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl ( (Meth) acrylate,
Selected from the group of halogenated monomers and monomers having siloxane groups.

  Examples of halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride.

Particularly most preferred halogenated monomers include fluorine olefins such as vinylidene fluoride, trifluorochloroethylene, tetrafluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, fluorinated or perfluorinated C ₃ -C as described in US2592069 and US27332370. ₁₁ -Carboxylic acid vinyl esters, (meth) acrylic esters of fluorinated or perfluorianted alcohols (eg fluorinated or fully fluorinated C ₃ -C ₁₄ -alkyl alcohols), eg US2642416, US32395557, BR1118007 Described in US Pat. No. 3,462,296

の（メタ）アクリル酸エステルを挙げることはできる。

(Meth) acrylic acid ester can be mentioned.

  Similarly, for example, glycidyl (meth) acrylate and formula I:

[However, R ¹ represents hydrogen, CH ₃ or C ₂ H _5,
R ² represents CH ₃ or C ₂ H ₅ ,
x is an integer of 4 to 12, particularly preferably an integer of 6 to 8,
y is an integer of 1 to 11, particularly preferably an integer of 1 to 6. ]
Or a copolymer of glycidyl (meth) acrylate and a vinyl ester of a fluorinated carboxylic acid.

  Useful copolymers further include, for example,

等のフッ化又は全フッ化Ｃ₃〜Ｃ₁₂−アルキルアルコールの（メタ）アクリル酸エステルと、
非ハロゲン化Ｃ₁〜Ｃ₂₀−アルコールの（メタ）アクリル酸エステル｛例、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、ｎ−エイコシル（メタ）アクリレート｝との共重合体も挙げることができる。

(Meth) acrylic acid esters of fluorinated or fully fluorinated C ₃ -C ₁₂ -alkyl alcohols such as
Non-halogenated C ₁ -C ₂₀ -alcohol (meth) acrylic acid ester {eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, 2- Mention may also be made of copolymers with ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl (meth) acrylate}.

  A review of suitable fluorinated polymers and copolymers can be found in, for example, M. Lewin et al. Chemical Processing of Fibers and Fabrics, Part B, Volume 2, Marcel Dekker, New York (1984), pages 172 et seq. Page 182.

  Furthermore, suitable fluorinated polymers are described, for example, in DE 199120810.

  From the group of olefins having a siloxane group, mention may be made, for example, of olefins represented by the following general formulas IIa to IIc:

[However, R ³ is
C ₁ -C ₁₈ - alkyl, for example methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- butyl, n- pentyl, isopentyl, sec- pentyl, neopentyl, 1,2-dimethyl Propyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl; preferably Is C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2- Dimethylpropyl, isoamyl, n-hexyl, isohe Hexyl, sec- hexyl; more preferably C ₁ -C ₄ - alkyl, for example methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- butyl; and among them methyl;
C ₆ -C ₁₄ - aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl Preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl;
C ₃ -C ₁₂ - cycloalkyl, such as cyclopropyl, cyclobutyl, cycloheptyl cyclopentyl, cyclohexyl, cycloheptyl cyclohexane, cyclooctyl, cyclononyl, cyclodecyl and cyclododecyl, preferably cyclopentyl, to cyclohexyl and or Si (CH _{3), 3}
Selected from.

R ¹ is as described above.

  n is an integer of 0-6, especially 1-2.

m is an integer from 2 to 10,000, in particular up to 100. ]
As a further useful polymer,
Polyethers such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran;
Polycaprolactone, polycarbonate, polyvinyl butyral,
Partially aromatic polyesters formed from aliphatic or aromatic dicarboxylic acids and / or aliphatic or aromatic dialcohols, for example, aliphatic dialcohols having 2 to 18 carbon atoms (eg, ethylene glycol, propanediol, 1 , 4-butanediol, 1,6-hexanediol, 1,8-octanediol or bisphenol A) and aliphatic dicarboxylic acids having 3 to 18 carbon atoms (eg, succinic acid, glutaric acid, adipic acid and α , Ω-decanedicarboxylic acid);
Mention may be made of polyesters formed from terephthalic acid and aliphatic dialcohols (eg ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol or 1,8-octanediol).

  The polyester can be terminated with, for example, a monoalcohol having 4 to 12 carbon atoms (eg, n-butanol, n-hexanol, n-octanol, n-decanol, or n-dodecanol).

  The polyester can be terminated with, for example, a monocarboxylic acid (eg, stearic acid).

Still useful polymers, melamine - mentioned also formaldehyde resins, urea - - formaldehyde resins, N, N-dimethylol-4,5-dihydroxy ethylene urea (may be etherified with alcohols which are C ₁ -C ₅₎ be able to.

  The molecular weight of the organic polymer can be selected from a wide range. The weight average molecular weight is generally 1000 to 10000000 g / mol, preferably 2500 to 5000000 g / mol. Molecular weight is measured by at least one of the following methods: light scattering, gel permeation chromatography (GPC), viscometer. When using a polymer selected from the group of polyolefins (eg polyethylene, polypropylene or polyisobutylene, further copolymers of ethylene and propylene, butylene or 1-hexene), the molecular weight is advantageously between 30,000 and 5,000,000 g / mol. .

  The width of the molecular weight distribution is not critical per se, but is usually in the range of 1.1-20. 2-10 are common.

  In one embodiment of the present invention, the ratio of the organic polymer is generally preferably at least 0.1 g / L of the liquid and at least 1 g / L of the liquid, and particularly preferably at least 10 g / L of the liquid. The maximum amount is, for example, 500 g / L, preferably 250 g / L, more preferably 100 g / L.

  In one embodiment of the present invention, the above organic polymer is not dissolved in the liquid. This insoluble in the organic polymer of the present invention means that the solubility in the liquid at room temperature is generally less than 1 g / L, preferably less than 0.1 g / L.

  One aspect of the present invention includes the use of at least two different organic polymers.

  In one embodiment of the present invention, the at least one organic polymer has a median particle size scale (median value, number average) of generally 0.1 to 50 μm, preferably 0.5 to 30 μm, more preferably 20 μm or less. Can be present in the form of particles.

  The at least one aqueous liquid used in the process of the present invention is at least 5.5 g / L, preferably 7 g / L, more preferably at least one particulate hydrophobic solid different from the above-mentioned polymer. It is contained at a rate of 10 g / L. When at least two kinds of particulate hydrophobic solids are used, it is preferable that at least one kind is present at a rate of 5.5 g / L. The maximum proportion of particulate hydrophobic solid is generally 150 g / L in total. The particulate hydrophobic solid may be inorganic or organic, but is preferably inorganic.

  Examples of suitable materials include polyethylene, polypropylene, polyisobutylene and polystyrene, as well as their copolymers, and one or more other olefins (styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide). Preferred polyethylene or polypropylene are described, for example, in EP-A 0 766 696.

  Particularly useful materials include inorganic materials, particularly solid inorganic oxides of the Groups 3-14 of the periodic table, carbonates, phosphates, silicates or sulfates such as calcium oxide, silicon dioxide or aluminum oxide, There may be mentioned calcium carbonate, calcium sulfate or calcium silicate, among which aluminum oxide or silicon dioxide is preferred. Silica dioxide in the form of silica gel is particularly preferred. Pyrolytic silica gel is highly preferred. The solid inorganic oxide can be rendered thermally hydrophobic by heating to 400-800 ° C., or is preferably thermally hydrophobized by a physically or chemically adsorbed organic or organometallic compound. For this reason, the particles are, for example, coated with an organometallic alkyllithium having at least one functional group (e.g. an alkyllithium compound such as methyllithium, n-butyllithium or n-hexyllithium) or silane ( Eg hexamethyldisilazane, octyltrimethoxysilane), in particular halogenated silanes (eg trimethylchlorosilane or dichlorodimethylsilane).

  Hydrophobicity in a particulate hydrophobic solid should be understood to mean that its solubility is generally less than 1 g / L, preferably less than 0.3 g / L (measured at room temperature).

The inorganic solid is preferably porous in nature. Most preferably, the porous structure is characterized by a BET surface area measured according to German standard DIN 66131. BET surface area of the inorganic solids used are generally 5~1000m ² / g, preferably from 10~800m ² / g, further 20 to 500 m ² / g are preferred.

    In one aspect of the invention, at least one of the hydrophobic solids is particulate. The median particle size scale (median value, number average) is generally at least 1 nm, preferably at least 3 nm, more preferably at least 6 nm. The maximum particle size (median value, number average) is generally 350 nm, and preferably 100 nm. The particle size can be measured using a commonly used method such as a transmission electron microscope.

  The mass ratio of organic polymer to organic or inorganic particulate solid is generally in the range of 9: 1 to 1: 9, in the range of 4: 1 to 1: 4, and further in the range of 7: 3 to 4: 6. preferable.

  In one embodiment of the invention, at least one hydrophobic solid is present in the form of spherical particles, and at least 75% by weight, preferably at least 90% is present in spherical form and the remaining particles are granules. Including particulate solids present in the form.

  In one embodiment of the invention, the at least one hydrophobic solid forms an aggregate. When one or more hydrophobic solids are present in aggregates (aggregates are composed of 2 to thousands of primary particles, each spherical), details regarding particle shape and dimensions relate to primary particles. .

  The at least one liquid used in the method of the present invention may contain at least one surfactant selected from the group of ionic or nonionic emulsifiers.

Useful nonionic emulsifiers, such as ethoxylated mono-, - di - and tri - alkylphenols (degree of ethoxylation: 3 to 50; alkyl radical: C ₄ -C _12), and ethoxylated fatty alcohols (degree of ethoxylation : 3-80; alkyl: C ₈ -C ₃₆₎ can be exemplified. Examples thereof include Lutensol ^R grade (manufactured by BASF Actuation Gesellshaft) or Triton ^R grade (manufactured by Union Carbide).

Useful anionic emulsifiers include, for example, alkali metal and ammonium salts of alkyl sulfate (alkyl group: C _{8 to} C ₁₂ ), ethoxylated alkanol (degree of ethoxylation: 4 to 30; alkyl group: C _{12 to} C ₁₈ ). Alkali metal and ammonium salts of sulfuric monoesters, alkali metal and ammonium salts of sulfuric monoesters of ethoxylated alkylphenols (degree of ethoxylation: 3 to 50; alkyl groups: C _{4 to} C ₁₂ ), alkyl sulfonic acids (alkyl groups: Mention may be made of alkali metal and ammonium salts of C _{12 to} C ₁₈ ) and alkali metal and ammonium salts of alkylaryl sulfonic acids (alkyl groups: C _{9 to} C ₁₈ ).

Useful cationic emulsifiers are generally C ₆ -C ₁₈ -alkyl-, C ₆ -C ₁₈ -aralkyl- or heterocyclic-containing primary, secondary, tertiary or quaternary ammonium salts, alkanol ammonium salts, Pyridinium salts, imidazolium salts, oxazolinium salts, morpholinium salts, thiazolinium salts, and further amine oxide salts, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, various 2- (N, N, N-trimethylammonium) ethyl paraffinic acid chlorides or acetates, N-cetylpyridinium chloride, N-laurylpyridinium sulfate. N-cetyl-N, N, N-trimethylammonium bromide, N-dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride, and Germin surfactant Mention may be made of N, N- (lauryldimethyl) ethylenediamine dibromide. A further example is H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen 198.

  Very particularly preferred examples include, for example, ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or at least one anhydride of α, β-unsaturated mono- or di-carboxylic acid ( Examples thereof include copolymers with acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, methylenemalonic acid, maleic anhydride, itaconic anhydride. The carboxyl group is, for example, an alkali metal ion, an alkaline earth metal ion, ammonium or amine (eg, triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine, N -Methyldiethanolamine, N- (n-butyl) diethanolamine or N, N-dimethylethanolamine).

  The ratio of the emulsifier in the liquid can be selected from a wide range, and can generally be selected from the range of 0.1 to 100 g / L, preferably from the range of 0.2 to 10 g / L.

  The process according to the invention is carried out by treating the textile material with at least one aqueous liquid. It is also possible to carry out a plurality of processing steps using the same or different liquids.

  In one embodiment of the present invention, the method of the present invention comprises treating the fabric with at least one organic polymer and further with an organic or preferably inorganic particulate solid, and then with the organic polymer, but the organic or inorganic It includes a step of treating with a new liquid that does not contain particulate solids.

  In one aspect of the invention, the method of the invention comprises treating the fabric with at least one organic polymer and further with an organic or preferably inorganic particulate solid, and then with another organic polymer, organic or A step of treating with a new liquid not containing inorganic particulate solids.

  In one aspect of the invention, the method of the invention comprises treating the fabric with at least one organic polymer and further with an organic or preferably inorganic particulate solid, and then without the organic polymer, the first step. And processing with a new liquid containing the inorganic particulate solid used in the above.

  The temperature at which the process of the invention is carried out is not critical per se. The liquid temperature is generally in the range of 10-60 ° C, preferably 15-30 ° C.

  The processing parameters of the method of the present invention are selected so that a wet pickup generally in the range of 25-85% by weight, preferably 40-70% by weight, can be produced by the method of the present invention. .

  The process according to the invention can be carried out on machines normally used for finishing textiles, for example pad-mangle. A vertical textile feed pad-mangle, in which the substantial element is two rolls in contact with each other and guides the fabric between them, is preferred. The liquid fills on the roll and wets the fabric. With pressure, the fabric is pinched and extruded, ensuring a certain adduct.

  In one embodiment of the present invention, the padding fabric conveying speed is generally in the range of 1-40 m / min, preferably in the range of 1-30 m / min.

  The treated fabric after treatment according to the invention can be dried by methods customary in the textile industry.

  The treatment of the present invention can be carried out after a heat treatment carried out continuously or batchwise. The time for the heat treatment can be selected within a wide range. The heat treatment can be performed in principle for about 10 seconds to about 30 minutes, preferably for about 30 seconds to about 5 minutes. The heat treatment is generally performed by heating to a temperature of 180 ° C. or lower, preferably 150 ° C. or lower. Of course, it is necessary to adapt the temperature of the heat treatment to the sensitivity of the fabric.

  As an example of a suitable method for the heat treatment, there is hot air drying.

  In one aspect of the invention, the woven material is provided with a tie layer prior to the treatment of the invention. The binding layer can be provided using a primer. The primer is preferably applied when finishing the dyed synthetic fiber.

  In one aspect of the invention, the tie layer applied to the textile material to be treated can be, for example, one or more polymers, in which case the synthesis of the polymer can also be carried out on the textile material. Particularly useful polymers have cross-linked or cross-linking groups, for example natural or synthetic polymers have free hydroxyl groups, carbonyl groups, primary or secondary amino groups or thiol groups. Examples of very useful polymers are lignin, polysaccharides, polyvinyl alcohol, and polyethyleneimine. Crosslinking is performed, for example, by a subsequent reaction with isocyanate, dimethylolurea or N, N-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU). Another particularly preferred crosslinking agent is a melamine-formaldehyde resin (which may be etherified with methanol).

  In another embodiment, when the polyester or polyamide is treated, 0.01 to 1% by mass, preferably 0.1 to 0.5% by mass of the fabric is treated with a strong base such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. Saponification by partial saponification.

The present invention further provides a textile material finished by the method of the present invention. In the finish of the present invention, the fabric of the present invention is provided with one or more coats. The textile material of the present invention exhibits particularly good dirt (sewage) and properties that keep water away (soil repellency, water repellency). The textile material of the present invention further exhibits a very good mechanical strength. In the textile material coated according to the invention, the solids used are distributed isotropically or substantially isotropic over the entire finish coating layer. That is, no concentration is seen in the boundary layer between the finish coating layer and the surrounding atmosphere. In one embodiment, the fabric of the present invention generally comprises a coating layer of 0.5 to 50 g / m ² , preferably 1 to 20 g / m ² , more preferably 1.5 to 10 g / m ² .

  The invention further relates to an aqueous liquid for finishing textile materials comprising at least one organic polymer and at least one organic or inorganic particulate solid, wherein the organic or inorganic solid is at least 5.5 g / There is also provided an aqueous liquid characterized by being present in the aqueous liquid in a proportion of L. The aqueous liquid of the present invention can contain additional components such as one or more organic solvents or one or more emulsifiers.

  The present invention also provides a method of using the liquid of the present invention to finish a textile material.

The present invention further provides a method for producing an aqueous liquid (hereinafter referred to as the production method of the present invention). The production method of the present invention comprises the following components:
At least one organic polymer;
At least one organic or inorganic particulate solid,
Water, and optionally one or more organic solvents, and optionally another component, such as one or more emulsifiers,
Mixing the amount of organic or inorganic particulate solid with the organic or inorganic solid selected to be present in the aqueous liquid at a rate of at least 5.5 g / L.

  The production method of the present invention is usually performed at a temperature ranging from room temperature to about 100 ° C., and room temperature is preferred.

  The process of the present invention generally includes a homogenization step, such as mechanical or pneumatic stirring, shaking, ultrasound, or a combination thereof.

  The order of adding the components can basically be freely selected. For example, the first step is performed by preparing a mixture of polymer and organic or inorganic solid that does not contain water and solvent, and then dispersing the dry mixture in organic solvent or a mixture of water and organic solvent or water. .

  In one embodiment of the process of the present invention, the starting step comprises a formulation comprising an organic polymer, an organic or inorganic particulate solid, optionally one or more organic solvents, and optionally one or more emulsifiers, and optionally further water. Prepare the product. Prior to carrying out the treatment of the textile material with the method according to the invention, the liquid according to the invention is produced by diluting the above-mentioned formulation with water. The formulation of the present invention preferably contains 15% by weight or less, preferably about 0.1-10% by weight, more preferably 5% by weight or less. The formulations of the present invention may also be free of water.

  The present invention further includes an organic polymer, an organic or inorganic particulate solid, optionally one or more organic solvents, and optionally one or more emulsifiers, and optionally water, and the proportion of water is about 0. Also provided is a formulation characterized in that it is 1-10% by weight, more preferably about 5% by weight.

  Examples illustrating the invention are given below.

[Example 1] (Production of the liquid of the present invention)
Example 1.1 (Production of liquid 1.1)
The following formulations were mixed in a flask by mechanical stirring:
883.5 ml of demineralized water,
62.4 g of an aqueous dispersion of a random copolymer (solid content 20% by mass) {this copolymer is 10% by mass of methacrylic acid and 90% by mass of the following compound:

から形成され、Ｍｎ３０００ｇ／モル（ゲル透過クロマトグラフィ）を有する｝、
１５．６ｇのランダム共重合体の水性分散液（固形分２０質量％）｛この共重合体は２０質量％のアクリル酸及び８０質量％のエチレンから形成され、Ｍｗ２００００ｇ／モルを有し、Ｎ，Ｎ−ジメチルエタノールアミンでｐＨ８．５と９．５の間に中和されている｝、及び
２５．２ｇのイソプロパノール。

And having a Mn of 3000 g / mol (gel permeation chromatography)},
15.6 g of an aqueous dispersion of a random copolymer (solid content 20% by weight) {this copolymer is formed from 20% by weight acrylic acid and 80% by weight ethylene, has a Mw of 20000 g / mol, N, Neutralized with N-dimethylethanolamine between pH 8.5 and 9.5}, and 25.2 g of isopropanol.

Thereafter, 13.3 g of dimethylsiloxane-modified pyrogenic silica {BET surface area: 225 m ² / g (measured according to German standard DIN 66131), primary particle size: 10 nm (median value, number average)} are added for 10 minutes in the mixture. Dispersion (Ultraturrax stirrer) gave an aqueous liquid 1.1.

Example 1.2 (Production of liquid 1.2)
The following formulations were mixed in a flask by mechanical stirring:
899.5 ml of demineralized water,
52.4 g of an aqueous dispersion of random copolymer (solid content 20% by weight) {This copolymer is 10% by weight methacrylic acid and 90% by weight of the following compound:

から形成され、Ｍｎ２９００ｇ／モル（ゲル透過クロマトグラフィ）を有する｝、
１４．６ｇのランダム共重合体の水性分散液（固形分２０質量％）｛この共重合体は２０質量％のアクリル酸及び８０質量％のエチレンから形成され、Ｍｗ２００００ｇ／モルを有し、Ｎ，Ｎ−ジメチルエタノールアミンでｐＨ８．５と９．５の間に中和されている｝、及び
２５．２ｇのイソプロパノール。

And has a Mn of 2900 g / mol (gel permeation chromatography)},
14.6 g of an aqueous dispersion of a random copolymer (solid content 20% by weight) {This copolymer is formed from 20% by weight acrylic acid and 80% by weight ethylene, has a Mw of 20000 g / mol, N, Neutralized with N-dimethylethanolamine between pH 8.5 and 9.5}, and 25.2 g of isopropanol.

Thereafter, 8.3 g of trimethylsiloxane-modified pyrogenic silica {BET surface area: 200 m ² / g (measured according to German standard DIN 66131), primary particle size: 10 nm (median value, number average)} is added, and 10 minutes in the mixture Dispersion (Ultraturrax stirrer) gave an aqueous liquid 1.2.

Example 1.3 (Production of liquid 1.3)
The following formulation was stirred in the flask by mechanical stirring:
884.5 ml of demineralized water,
66.3 g of an aqueous dispersion of random copolymer (solid content 20% by mass) {this copolymer is 10% by mass of methacrylic acid and 90% by mass of the following compound:

から形成され、Ｍｎ３０００ｇ／モル（ゲル透過クロマトグラフィ）を有する｝、
１３．８ｇのランダム共重合体の水性分散液（固形分２０質量％）｛この共重合体は２０質量％のアクリル酸及び８０質量％のエチレンから形成され、Ｍｗ２００００ｇ／モルを有し、Ｎ，Ｎ−ジメチルエタノールアミンでｐＨ８．５と９．５の間に中和されている｝、及び
３０．２ｇのイソプロパノール。

And having a Mn of 3000 g / mol (gel permeation chromatography)},
13.8 g of an aqueous dispersion of random copolymer (solid content 20% by weight) {This copolymer is formed from 20% by weight acrylic acid and 80% by weight ethylene, has a Mw of 20000 g / mol, N, Neutralized with N-dimethylethanolamine between pH 8.5 and 9.5}, and 30.2 g of isopropanol.

Thereafter, 5.2 g of dimethylsiloxane-modified pyrogenic silica {BET surface area: 225 m ² / g (measured according to German standard DIN 66131), primary particle size: 10 nm (median value, number average)} are added for 10 minutes in the mixture. Dispersion (Ultraturrax stirrer) gave an aqueous liquid 1.3.

Example 1.4 (Production of liquid 1.4)
The following formulation was stirred in the flask by mechanical stirring:
886.3 ml of demineralized water,
20.8 g of an aqueous dispersion of random copolymer (solid content 20% by mass) {this copolymer is 10% by mass of methacrylic acid and 90% by mass of the following compound:

から形成され、Ｍｎ３０００ｇ／モル（ゲル透過クロマトグラフィ）を有する｝、
５７ｇのランダム共重合体の水性分散液（固形分２０質量％）｛この共重合体は２０質量％のアクリル酸及び８０質量％のエチレンから形成され、Ｍｗ２５０００ｇ／モルを有し、Ｎ，Ｎ−ジメチルエタノールアミンでｐＨ８．５と９．５の間に中和されている｝、及び
２８．４ｇのイソプロパノール。

And having a Mn of 3000 g / mol (gel permeation chromatography)},
57 g of an aqueous dispersion of a random copolymer (solid content 20% by weight) {This copolymer is formed from 20% by weight acrylic acid and 80% by weight ethylene, has a Mw of 25000 g / mol, N, N- Neutralized with dimethylethanolamine between pH 8.5 and 9.5}, and 28.4 g isopropanol.

Thereafter, 7.5 g of dimethylsiloxane modified pyrogenic silica {BET surface area: 225 m ² / g (measured according to German standard DIN 66131), primary particle size: 10 nm (median value, number average)} is added for 10 minutes in the mixture. Dispersion (Ultraturrax stirrer) gave an aqueous liquid 1.4.

[Example 2] (Textile finish)
Example 2.1
A polyester woven fabric having a basis weight (basis weight) of 220 g / m ² was treated with the liquid 1.1 on a padder (Mathis, model HVF12085). The squeezing pressure of the roll was 2.6 bar. This produced a 60% wet pickup. The coating speed was 2 m / min. The treated polyester woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyester woven fabric 2.1 was obtained.

Example 2.2
A polyamide woven fabric having a basis weight (basis weight) of 160 g / m ² was treated with the liquid 1.1 on a padder (Mathis, model HVF12085). The squeezing pressure of the roll was 2.6 bar. This produced a 65% wet pickup. The coating speed was 2 m / min. The treated polyamide woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyamide woven fabric 2.2 was obtained.

Example 2.3
A polyacrylic woven fabric with a basis weight (basis weight) of 295 g / m ² was treated with liquid 1.1 on a padder (Mathis, model HVF12085). The squeezing pressure of the roll was 2.6 bar. This produced a 50% wet pickup. The coating speed was 2 m / min. The treated polyacrylic woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyacrylic woven fabric 2.3 was obtained.

Example 2.4
The polyester fabric of basis weight of 220 g / m ² (basis weight), padder (Mathis Co., Model HVF12085) was treated with liquid 1.2 on. The squeezing pressure of the roll was 2.6 bar. This produced a 60% wet pickup. The coating speed was 2 m / min. The treated polyamide woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyester woven fabric 2.4 was obtained.

Example 2.5
A polyamide woven fabric having a basis weight (basis weight) of 160 g / m ² was treated with liquid 1.2 on a padder (Mathis, model HVF12085). The squeezing pressure of the roll was 2.6 bar. This produced a 65% wet pickup. The coating speed was 2 m / min. The treated polyamide woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyamide woven fabric 2.5 was obtained.

Example 2.6
A polyacrylic woven fabric with a basis weight (basis weight) of 295 g / m ² was treated with liquid 1.2 on a padder (Mathis, model HVF12085). The squeezing pressure of the roll was 2.6 bar. This produced a 50% wet pickup. The coating speed was 2 m / min. The treated polyamide woven fabric was then dried with a 120 ° C. tenter. The final heat treatment was performed at 150 ° C. for 3 minutes using circulating air. A treated polyacrylic woven fabric 2.6 was obtained.

3. Water Repellency Test of Fabric Samples Treated According to the Present Invention A flat wood that can be continuously adjusted in a range of 1 ° to 90 ° of a fabric sample to be tested treated according to the present invention by hand pulling Fixed to the board with nails. Thereafter, a single water drop was dropped onto the fabric sample from a height of 10 mm using a cannula. The water droplet had a mass of 4.7 mg. The inclination angle was gradually increased to gradually increase to an inclination angle at which the ball began to move and no trace of adhesion was observed. The results are shown in Table 1.

Claims (12)

At least one copolymer using at least 50% by mass of a fluorinated olefin as a hydrophobic monomer, and at least one organic or inorganic particulate solid having a median particle size (number average) in the range of 1 to 350 nm. And a copolymer of ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or at least one α, β-unsaturated mono- or di-carboxylic acid anhydride. A method of finishing a textile material by treating the textile material with at least one aqueous liquid comprising at least one emulsifier, wherein the organic or inorganic solid is at least 5.5 g / L. A method characterized in that it is present in the aqueous liquid in a proportion.   The method of claim 1, wherein the at least one organic or inorganic solid is hydrophobic.   3. A method according to claim 1 or 2, wherein a tie layer is provided on the surface of the fabric prior to treatment.   The method according to claim 1, wherein the solid is at least one inorganic solid.   The method according to any one of claims 1 to 4, wherein an organic or inorganic solid is present in the aqueous liquid at a rate of at least 7 g / L.   The method according to any one of claims 1 to 5, wherein the organic or inorganic solid has a particle size (median value, number average) in the range of 1 to 350 nm.   A textile material finished by the method according to any one of claims 1-6. At least one copolymer using at least 50% by mass of a fluorinated olefin as a hydrophobic monomer, and at least one organic or inorganic particulate solid having a median particle size (number average) in the range of 1 to 350 nm. And a copolymer of ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or at least one α, β-unsaturated mono- or di-carboxylic acid anhydride. An aqueous liquid comprising at least one emulsifier, wherein an organic or inorganic solid is present in the aqueous liquid at a rate of at least 5.5 g / L.   A method of using the aqueous liquid of claim 8 to finish a textile material. The following ingredients:
At least one copolymer using at least 50% by mass of a fluorinated olefin as a hydrophobic monomer;
At least one organic or inorganic particulate solid having a median particle size (number average) in the range of 1 to 350 nm,
Selected from copolymers of ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or anhydride of at least one α, β-unsaturated mono- or di-carboxylic acid At least one emulsifier,
A method for producing an aqueous liquid according to claim 8 by mixing water, and optionally one or more organic solvents, and optionally another component comprising:
A method characterized in that the amount of organic or inorganic particulate solid is selected such that the organic or inorganic particulate solid is present in the aqueous liquid at a rate of at least 5.5 g / L. A method of using a formulation to produce the aqueous liquid of claim 8, comprising:
At least one copolymer having at least 50% by weight of a fluorinated olefin as a hydrophobic monomer, at least one organic or inorganic having a median particle size (number average) in the range of 1 to 350 nm. A particulate solid, optionally one or more organic solvents, ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or at least one α, β-unsaturated mono- or di- A method of use, comprising at least one emulsifier selected from a copolymer with an anhydride of carboxylic acid, and further optionally water, and the proportion of water being 15% by mass or less. A copolymer using at least 50% by mass of a fluorinated olefin as a hydrophobic monomer , an organic or inorganic particulate solid having a median particle size (number average) in the range of 1 to 350 nm, and optionally one or more organic solvents, And a copolymer of ethylene and at least one α, β-unsaturated mono- or di-carboxylic acid or at least one α, β-unsaturated mono- or di-carboxylic acid anhydride. A formulation characterized by comprising at least one emulsifier and, optionally, water, and the proportion of water being 15% by mass or less.